Perfluoroalkyl-substituted triazines



United States Patent 3,128,272 PERFLUOROALKYL-SUBSTITUTED TRIAZINESRobert L. Wear, West St. Paul, and Arthur H. Ahlbrecht,

White Bear Lake, Minn., assiguors to Minnesota Mining and ManufacturingCompany, St. Paul, Minn., a corporation of Delaware No Drawing. FiledJune 11, 1957, Ser. No. 664,911

9 Claims. (Cl. 260-249.6)

in which R is alkylamino, arylamino, alkoxy, and aryloxy may be reactedwith formaldehyde to yield polymethylol derivatives, which in turn maybe condensed to thermosetting crosslinked polymeric products. Suchcompounds and polymers are disclosed in US. Patents Numbers 2,197,357,2,392,607, 2,392,608, 2,392,649, 2,393,754, 2,418,336, and 2,731,438.The polymeric products described therein have been of special interestbecause of the relative ease with which a wide variety of properties maybe attained through suitable selection of the substituent R. Thus with Rrepresenting a long chain alkylamino or alkoxy group, the near-maximumdeviation from the harder, more brittle characteristics of theunmodified triamino triazineformaldehyde condensate polymer is attained,thus producing flexible resins. By suitable modification of the N-alkylsubstituent of the triamino triazine it has also heretofore beenpossible to obtain an enhanced degree of water repellency as comparedwith the formaldehyde condensate of the corresponding unsubstitutedcompound. However, the advantages attained in the direction of waterrepellency of these triazineformaldehyde condensates were brought aboutheretofore only with concomitantly increased oil sensitivity orwettability, and no adequate solution to this problem has heretoforebeen available.

Additionally, it has heretofore been possible to prepare certaintri(polyfiuoroalkyl)cyanurates, as disclosed in US. Patent 2,741,606.These compounds are, however, incapable of condensing with aldehydes toform polymeric substances.

This invention has as one object the provision of new and novelfluorocarbon-substituted amino-triazines which can be condensed withformaldehyde to yield polymeric products of marked oil repellency. Anadditional object of the invention is to provide thermosetting polymerspossessing both oil and water repellent characteristics. A furtherobject of the invention is to provide surface coating compositions ofenhanced oil and water repellent characteristics. A still further objectof the invention is to provide curing agents for oxirane type resinswhich will enhance ,the oil and water repellency of such resins.

In accordance with the above objects, and other objects of the inventionwhich will become evident hereinafter, it has been found that certainsubstituted symmetrical triazines which can be represented by theformula ICC.

wherein X and Y are chosen from the group consisting of amino andhydrazino radicals, R is a perfluoroinated alkyl radical having 4 to 12carbon atoms, and QW is a linking group, in which Q is a member of thegroup consisting of divalent sulfonyl, carbonyl and methylene radicals,and when Q is sulfonyl, W is a divalent radical of the group consistingof -NH(CH ),,NH-, and -NR, wherein n is an integer from 1 to 12 and R ishydrogen or a lower alkyl radical; when Q is carbonyl, W is a divalentradical of the group consisting of --NH (CH NH- and 'NH, wherein m is anumber from 0 to '12; and when Q is a methylene radical, W is a divalentradical of the group consisting of ,(CH O?- and wherein m is a numberfrom 0 to 12, and the condensation products thereof with formaldehyde,possess particular utility with regard to oil and water repellency.

The compounds of the invention are further illustrated by compounds ofthe above general formula, in which the components Q and W of thelinking group taken together are designated as Z, and Z is one of thedivalent radicals 2)qwherein n is an integer from 1 to 12, m is a numberfrom 0 to 12, q is an integer from 1 to -13, and R is a member of thegroup consisting of hydrogen and lower alkyl radicals.

The following compounds having the above-mentioned linking groupsfurther illustrate the scope of the above general formula:2,4-diamono-6- (perfluorododecanoyl hydrazido) -s-trizine,2,4-diamino-6- l, l-dihydroperfluorododecyloxy) -s-triazme2,4-diamino-6- (N-methyl-perfluorododecanesulfonamido)-s-triazine,

2,4-diamino-6-( 1, l-dihydroperfluorododecyl amino) -s-triazme,

2,4-diarnino-6- 3-oxal l-dihydroperfluorohexyloxy) -striazine,

2,4-diamino-6-.(3:0xa-l,1,2,2 tetrahydroperfluorohexyloxy -s-triazine2,4-diamino-6-( 1, l-dihydroperfluoroethoxy) -s-tr-iazine,

2,4-diamino-6- w-perfluorooctylundecyloxy) -s-triazine,

2,4-dihydrazino-6-( 1,1-dihydroperfluoropropoxy)-s-triazine,

2-amino-4-hydrazi no-;6-(.N-propyl-perfluorohexanesulfonamido)-s-triazine,

2,4-dihydrazino-6-(N-ethyl-perfluorododecanesulfonamido -s-triazine,

2,4-dihydrazino-6- (perfluorobutanoylhydrazido) -s-triazine.

Broadly speaking, the linking groups employed in the present inventionare introduced by several methods each of which is adapted to theparticular type of compound, as will be apparent hereinafter. Thus,suitable fluorinated compounds can be condensed with a mono-halogenatedtriazine derivative or a halogen derivative of the fluorinated compoundcan be condensed with a suitable derivative of the selected triazine.For example, those compounds which contain carboxylic hydrazide groupsin the linking group can be made by condensing a per- 3 4 fiuorinatedacid halide or ester with hydrazine or substiemployed instead of thesulfonyl halide in these reactions. tuted hydrazine and then furthercondensing the resultant Perfluoroalkanesulfonamides are condensed withcyahydrazide, for example with 6-chloro-2,4-diamino-s-trinuric chlorideby the reactions illustrated by the following azine (formed by partialreaction of commercially availequations, wherein R andR again have thesignificance able cyanuric chloride with ammonia, as described in thedescribed hereinabove: Journal of the American Chemical Society, volume73, R N R N pages 2981-2983). In this case the acid halide may be Rso 1IH 01 O COI- RSO l ro col a chloride or fluoride of a carboxylic acidcontaining the T- H I H selected perfluorinated group. The formation ofamides N of fluorinated carboxylic acids by this method has been 10 jdisclosed by Diesslin and Kauck in U.S. Patent 2,567,011 g I and offluorinated sulfonic acids by Brice and Trott in U.S. Patent 2,732,398.The reactions are illustrated by NHs/ l Z Z the following equationswherein R has the same signifi- R /N R N cance as heremabove: RfSOFDIFC/RfCOF HzNNH R C0-NHNHq HF l I I I I i I i N f 9 RtCONHN 2 01- ({f-NH:NH: NHNHZ Those compounds in which a plurality of methylene groups areinterposed between the perfiuoroalkyl group NHz and an hydroxyl orcarboxylic acid group are available by first desulfonylatively reactinga perfluoroalkanesulfonyl RiC0-NHNHC C NH2 chloride or perfiuoroalkyliodide with a distally unsatul Q, rated alkenol, alkenoic acid or estersthereof followed by reductive dehydrohalogenation and, if needed,saponification to furnish the desired materials. The distally per- N zfluoroalkylatcd alkanols and also the corresponding perfluoroalkylamines are available by reduction respectively The1,1-dihydroperfiuoroalkyl amines and alcohols deof the correspondingacids perpared as above or of the scribed by Husted and Ahlbrecht inU.S. patents numamides thereof, these latter reactions being analogousto bered 2,691,043 and 2,606,797, respectively, and distally those morefully described in U.S. patents numbered perfluorinated alkanols andalkyl amines hereinafter de- 2,666,797 and 2,691,043. schematically, thereactions scribed condense with 6 chloro 2,4-diamino-s-triazine 3leading to these intermediates can be illustrated by the analogously.following equations, wherein Rf has its usual significance Alkyenediamines are incorporated in the linking group as herein employed:

Raney/N 3 R,0H,0H,-0H,C 0 H R;CH OH CH OOCl RiCH3CH5CHgCONHg l l LiAlH4Rr-CHzCHz-CH C OgCH: RgCHzCHzOHz-CH;NH

H, 0 e ch ro itiie r RgOH -OH;CH -CH OH as shown in the followingequation in which R and n Suitable catalysts for effecting thecondensation of the have the same significance as set forth herein:perfluoroalkanesulfonyl halide and the unsaturated acid are, forexample, organic and inorganic peroxides, azo N compounds, actinic lightand the like, although heating H the reactants alone, over a relativelylonger period of H2N*(CH) N time, will accomplish the desired result.

\ N The perfluoroalkyl group-containing triazines of the invention areuseful intermediates for the preparation of 1 polymeric substances bycondensation with formaldehyde. 2 H N The polymeric materials thusproduced are thermosetting resins which exhibit oil and water repellentcharacteristics.

l HZN (CH) N (|J ii Thus, they can be cast in the form of thin sheets orfilms which have these properties, or they can be employed as coatings;for example on fibrous substrates such as paper 1 and the like, toimpart oil and water repellency thereto.

a Additionally, the substituted triazines of the invention RisOacll canbe used as curing agents for epoxy resins, whereby the N cured resinshave increased oil and water repellency. H H The following examples willmore specifically illustrate I z- 2)I- z the preparation and propertiesof the compounds of the 1; L; invention. As examples, they are to beconsidered as non-limiting in their descriptive aspects.

1 EXAMPLE I A mixture of about 27 g. (0.18 mole) 2,4-diamino-6-Perfluorinated carboxylic acid esters and halides can bechloro-s-triazine and g. (0.375 mole) of 1,1-dihydroperfluorooctylalcohol is refluxed with 7 g. (0.18 mole) of sodium hydroxide for 2hours. The reaction mixture is then cooled and is poured into about oneliter of diethyl ether. The desired2,4-diamino-6-(1,1-dihydroperfluorooctoxy-s-triazine formed in thereaction precipitates and is isolated by filtration. Afterrecrystallization from ethanol, the2,4-diamino-6-(1,l-dihydroperfiuorooctoxy)striazine thus prepared meltsat about 1745 C.

Analysis-Found: 26.0% C, 55.4% F. Calculated: 26.0% C, 56.0% F.

When the procedure of this example is repeated, using correspondingamounts of 1,1-dihydroperfluoropentanol, 1,l-dihydroperfluorononanol or1,1-dihydroperfluorododecanol (all of which are prepared as described inUS. Patent 2,666,797), there are obtained, respectively, 2,4- diamino-6-1,1-dihydroperfluoropentoxy)-s-triazine, 2,4-diamino-6-(1,l-dihydroperfluorononoxy)-s-triazine and 2- 4-diamino-6-l,1-dihydroperfluorododecoxy) -s-triazine.

Fluorinated alcohols containing perfluorinated tails attached to theomega carbon atom of an alkanol can be prepared by known methods; forexample, by reduction of the corresponding fluorocarbon monocarboxylicacids with lithium aluminum hydride in ether solution. This and othermethods for accomplishing the reduction are described in US Patent2,732,370. The distally perfluoroalkylated aliphatic acids employed asstarting materials can be prepared by condensation of aperfluoroalkanesulfonyl halide with a terminally unsaturated aliphaticacid, followed by reductive dehydrohalogenation in the presence of Raneynickel catalyst. The reaction is exemplified by the preparation of5-perfluorooctylpentanoic acid, as follows:

A mixture of 26.8 g. (0.052 mole) of perfluorooctanesulfonyl chlorideand 5.0 g. (0.050 mole) of 4-pentenoic acid (allyl-acetic acid) isrefluxed for about four hours at about 120-145 in the presence of acatalytic amount (1.0 g.) of (ii-tertiary butyl peroxide. The reactionmixture is fractionally distilled under reduced pressure and thefraction boiling at about 100 C. at 0.010 mm. is collected. Afterrecrystallization from a mixture of chloroform and carbon bisulfide, the4-chloro-5-(perfiuorooctyl) pentanoic acid thus prepared melts at about89-90 C. The 4-chloro-5-(perfluorooctyl)-pentanoic acid thus prepared ishydrogenated by shaking a solution of 8.00 g. (0.0145 mole) of the acidand 2.5 g. (0.062 mole) of sodium hydroxide in a mixture of 30 ml. ofwater and 30 ml. ethanol for 3 hours at 140 C. in a rockinghigh-pressure hydrogenation apparatus in the presence of 4 g. Raneynickel catalyst and with hydrogen supplied at 2500 p.s.i. pressure.After removal of the catalyst, evaporation to dryness, solution of theresidue comprising sodium perfiuorooctyl pentanoate in water andacidification of the resulting solution, the saturated perfluoroalkylaliphatic acid formed by hydrogenation is isolated as a waxy whiteprecipitate, which can be distilled at 100 C. at 0.02 mm. pressure.After recrystallization from carbon bisulfide, theS-(perfluorooctyl)-pentanoic acid thus prepared melts at about 86.587.3C.

The S-(perfluorooctyl)-pentanoic acid thus prepared is converted toS-(perfluorooctyl)-pentanol by lithium aluminum hydride reduction, asset forth above.

When 5-(perfluorooetyl)-pentanol is employed in the procedure usedhereinabove, in place of 1,1-dihydroperfluorooctanol, there is obtained2,4-diamino-6-(5-perfiuorooctyl-pentanoxy) -s-triazine.

EXAMPLE H 106 g. (0.2 mole) of the sodium salt ofN-methyl-perfluorooctane sulfonamide are reacted with a solution of 37g. (0.2 mole) of cyanuric chloride in 400 ml. of acetone at 5 C. forabout 90 minutes and then stirred at room temperature for about 3 hrs.The reaction mixture is filtered and the 2(N-methyl-perfluorooctanesulfonarnido)- 4,6-dichloro-s-triazine formed in the reaction isisolated from the filtrate by evaporation of the acetone. Afterrecrystallization from carbon tetrachloride the product melts at about102-104 C. Sixty g. of 30% aqueous ammonia and 20.5 g. (0.03 mole) ofthe substituted triazine thus prepared are then inter-reacted in astainless steel autoclave under autogenous pressure at 125 C. Thechlorine atoms are thus replaced by two amino groups to furnish2,4-diamino-6-(N-methyl-perfluorooctanesulfonamido)-s-triazine, which isisolated by evaporation of the aqueous solution to dryness andrecrystallization of the residue from methanol. The product melts atabout 182-184 C. Calculated for C H F SO N C, 23.2%, F, 51.9%. Found: C,23.2%; F, 52.1%.

The sulfonamide from which the sodio derivative employed as a startingmaterial in this example is formed can be obtained by the process of US.Patent No. 2,732,- 398 which patent also discloses other suitablefluorinated compounds useful as starting materials for the compounds ofthe present invention.

N-alkyl-perfluoroalkyl sulfonamides can also be obtained by the methoddescribed in the application of Ahlbrecht et al., Serial No. 560,900,now US. Patent 2,803,- 615. The preparation ofN-n-propyl-perfluorooctanesulfonamid'e illustrates this method, asfollows:

A flask equipped with a thermometer, stirrer and distilling head issuccessively charged with about 10 liters of isopropyl ether, 1.6 kg. ofn-propylarnine, and then With 4,544 grams of perfluorooctane sulfonylfluoride previously purified by washing twice with pyridine, followed bya dilute hydrochloric acid Wash and a water wash, drying over magnesiumsulfate, treating with decolorizing activated carbon, and filtering. Thelatter material is added over a period of 1 /2 hours with constantstirring to maintain the temperature at about 25-30 C. and for 2 hoursat 40 C. After cooling to room temperature, the mixture is washed withabout 4.5 liters of 9% aqueous hydrochloric acid solution. The acidwashings are separated and the product is rewashed with about 4.5 litersof an aqueous solution containing 4.5% hydrochloric acid and 4% ferroussulfate, and the aqueous phase is again removed. The reaction flask isfitted with a distilling head, and the ether is removed by distillationunder reduced pressure at a Water bath temperature of 7080 C., yieldingN-propyl-perfluorooctane sulfonamide represented by the formula:

The sodium salt is prepared by dissolving 4.6 kg. of this amide productin about 5 liters of absolute methanol, adding 474 grams of sodiummethoxide (CH ONa) in 2,300 ml. of absolute methanol, and removing thealcohol by distillation of the reaction mixture under reduced pressureat a bath temperature of 7080 C.

When the sodium salt of N-n-propyl-perfluorooctanesulfonamide isemployed in the procedure of this example, in place of thesodio-derivative of N-methyl-perfluoro-octane-sulfonamide, there isproduced the corresponding 2,4- diamino 6 (N n propylperfluorooctanesulfonamido) -s-triazine.

EXAMPLE III Following the procedure of Example 11, a solution of 15 g.(0.041 mole) of the sodium salt of N-methyl-perfiuorobutanesulfonamidein 30 ml. of acetone is added slowly and with stirring to a solution of7.6 g. (0.041 mole) of cyanuric chloride in 40 ml. of acetone at about20 C. Thereis a slight evolution of heat and the mixture is allowed tostand at ambient temperature for about 1 hour. The precipitate of sodiumchloride which forms is removed by filtration and washed with a smallamount of acetone. The combined filtrate and washings are evaporated onthe steam bath, yielding as a residue a waxy solid to which is added 60ml. of 28% aqueous ammonia. After the somewhat exothermic initialreaction, this mixture is heated in a stainless steel autoclave at l10C. for three hours. The product, 2,4- diamino 6(N-methyl-perfluorobutanesulfonamido)-striazine, precipitates and iscollected by filtration, washed with water and recrystallized frommethanol. The 2,4- diamino 6(N-methyl-perfluoro-butanesulfonamido)-striazine thus prepared melts atabout 150 C. and contains no detectible chlorine. Analysis: calculated37.7% F; found, 38.7% F. The compound is useful as a curing agent forepoxy-type resins.

EXAMPLE IV 2,4 dihydrazino-6-(1,1-dihydroperfluorohexylamino)-s-triazine is prepared by reacting 9.5 g. (0.05 mole) of cyanuricchloride, 15 g. (0.05 mole) of 1,1-dihydroperfluorohexylamine and 2.7 g.(0.025 mole) of anhydrous sodium carbonate in a mixture of 20 g. ofdioxane and 30 g. of water at C. for about 1 hour. To the reactionmixture are then added 23 g. (0.4 mole) of 85% hydrazine hydrate and themixture is refluxed for about 2 hours. On cooling, the2,4-dihydrazino-6-(1,1- dihydroperfiuorohexylamino)-s-triazineprecipitates, and is collected by filtration. Without furtherpurification the product melts at 193208 C. Analysis of the materialthus prepared showed 22.4% N, 50.0% F, 25.1% C; calculated for CgHqFllNg25.6% N, 47.7% F, 24.7% C. This product readily reacted with thebisphenol A-epichlorohydrin epoxy-resin (available commercially underthe trade mark Epon 828), when mixed therewith and heated, to give afirmly cured product. This utility as a curing agent for epoxy-typeresins is characteristic of the several compounds of this invention.

EXAMPLE V 2,4 diamino-6- (perfluorooctanoylhydrazido) -s-triazine isprepared by the reaction of 8.6 g. (0.02 mole) of perfluorooctanoic acidhydrazide with 3.0 g. (0.021 mole) of 2,4-diamino-6-chloro-s-triazine in150 ml. water by slow addition thereto of 0.8 g. (0.02 mole) of sodiumhydroxide (dissolved in 10 ml. of water) during a reflux period of about2 hours followed by cooling. The product is obtained as a precipitate ofcrude material which is recrystallized from 80% aqueous ethanol. The2,4- diamino 6-(perfluorooctanoylhydrazido)-s-triazine thus preparedmelts at about 259260 C. The use of this substance to produce aformaldehyde condensate resin is carried out in a manner analogous tothat disclosed in the following example, and there is produced a hard,insoluble and oleophobic resin.

EXAMPLE VI Two grams of2,4-diamino-6-(N-methyl-perfluorooctanesulfonamido)-s-triazine preparedby the procedure of Example III are refluxed for about 1.5 hours with 10g. of 37% aqueous formaldehyde. The reaction mixture is evaporated todryness and the residual resin is dissolved in about 50 ml. of dioxane.Films cast from this solution can be cured at 165 C. for about 30minutes to give a hard, insoluble, oleophobic, heat resistant polymer.The curing time can be shortened by adding a catalyst, for example,maleic anhydride or oxalic acid.

EXAMPLE VII A mixture of 6.2 g. of2,4-diamino-6-(N-methylperfluorooctanesulfonamido)-s-triazine, 3.2 g. of37% aqeuous formaldehyde and 12 g. of butanol-l is refluxed for 4 hoursunder a Barret trap which serves to remove the water initially presentand formed in the reaction. The solution of resin thus formed is dilutedwith about 90 ml. of dioxane and about 0.05 g. of maleic anhydride isadded thereto as a catalyst. Polymer films cast from this solution andthoroughly cured at 165 C. are hard and brittle and show averageadvancing contact angles of 109 and 54 to water and hexadecane,respectively, and average receding contact angles of 92 and 48respectively.

These results clearly demonstrate the hydrophobic and oleophobicproperties of this resin since wetting is indicated by an angle of 0.

8 EXAMPLE VIII In a procedure analogous to that of Example VII, 1.5 g.of 2,4-diamino-6-(l,1-dihydroperfluorooctoxy-s-triazine is condensedwith formaldehyde by refluxing for about 2 hours with 20 g. of a 37%aqueous formalin solution, followed by dehydration. A polymer isproduced which is soluble in dioxane and is cured by heat either in thepresence or absence of maleic anhydride to a hard, brittle insolublepolymer of value as in inert protective coating for metal surfaces. Forthe purpose of coating metal it is applied as a solution in a suitablesolvent, for example, dioxane, and then baked in the usual way.

The 2,4 dihydrazino 6-(1,1-dihydroperfiuorohexylamino)-s-triazineproduced in Example V is condensed with formaldehyde by the procedure ofExample VII. A water insoluble, oleophobic resin, curable by heating, isthus produced.

EXAMPLE IX A mixture of 4.5 g. (0.01 mole) of 2,4-diarnino-6-(N-gnethyl-perfluorobutanesulfonamido)-s-triazine produced by the method ofExample IV and 3.3 g. (0.04 mole) of 37% aqueous formaldehyde in 5 ml.of dioxane is refluxed for 2.5 hours. The resulting solution is usabledi rectly for casting films. Such a film, baked for 2 hours at 120 C.,is perfectly clear and transparent, glossy, hard and brittle and showsadvancing contact angles of from 54 to 96 and 0 to 28 to water andhexadecane, respectively. The receding contact angles measured variedover different parts of the film when in contact with water and were 0for contact with hexadecane.

The resins of this invention confer valuable hydroprobic and oleophobicproperties on fibrous webs, such as textiles. Hydrophobic properties aremeasured by Standard Spray List Ratings of 0, 50, 70, 80, and 100determined by Method 2252 of the American Association of TextileChemists and Colorists and described, for example, on pages 136 to 138inclusive of the Technical Manual and Yearbook of that association forthe year 1954. It is to be noted that this method provides for nointerpolation of results which are reported as one of the above sixratings.

Oleophobic properties are measurable by means of ratings assigned on thebasis of resistance for 3 minutes to drops of mixtures varying by 10%increments from pure mineral oil (Nujol, Stanolind, etc.) to pureturpentine applied gently to the surface of the textile maintained leveland are indicated by numerals 0 to 10 respectively for the mixture ofhighest turpentine content which fails to penetrate. Thus the numeral 5indicates a mixture of 50% of each of the two components. Interpolationis judged visually and indicated where significant by means of plus orminus signs.

EXAMPLE X Swatches of clean cotton cloth about 6" square are impregnatedby padding with solutions of the indicated concentrations of the resinof Example IX. After drying to remove dioxane the samples are cured forthe times and at the temperatures indicated and tested and assignedspray ratings and oil resistance ratings. The tests are repeated after astandard laundering cycle of 1 hour in a Launder-ometer at F. Theresults of the tests are as follows:

Treated Cotton Cure Spray Rating Oil Resistance Rating Concentration ofresin in dioxane Time Temp., Cured Laun- Cured Laun- (nun) C. dereddered Untreated cotton cloth, used as a control, shows substantiallyzero rating in both spray and oil resistance tests before and afterlaundering.

A polyethylene glycol terephthalate fabric treated in a similar mannerwith a 1.5% solution of the resin of Example VII and cured minutes at130 C. and tested in the same way rates 80 for spray resistance and 10+for oil resistance. A cotton fabric treated in this manner rates 90 forspray resistance and 7 for oil resistance.

Similarly, solutions of other resins of this invention, as for examplethose disclosed in Examples VIII and IX, impart desirable hydrophobicand oleophobic properties to textiles such as cotton, wool, linen, silkand synthetic fibers. Similar treatments are also applicable to suchnonwoven mats or Webs of fibers as paper and felt.

EMMPLE XI The dihydrazino compounds exemplified by the2,4-dil1yrazino-6-( 1, l-dihydroperfluorohexyl amino) -s-triazineprepared by the process of Example V effectively cure epoxy (oxirane)resins such as bisphenol A-epicholohydrin resins. The new curing agentsof the present invention thus provide a novel method of introducingchemically bound perfluoroalkyl groups into epoxy resins.

For curing a typical epoxy resin, 2,4-dichloro-6-(N-methyl-perfiuorooctanesulfonamido) s triazine is converted to thecorresponding 2,4-dihydrazino compound by heating 20 g. (0.03 mole) ofthe former with 30 g. (0.5 mole) of 85% hydrazine hydrate in 20 ml. ofwater at 90 C., while adding a solution of 2.4 g. (0.06 mole) of sodiumhydroxide in ml. of water thereto over a period of 2 hours. The productis collected and washed thoroughly with water. After drying, the2,4-dihydrazino- 6-(N-methyl-perfluoroctanesulfonamide) s triazine thusprepared melts at about 185 C.

Analysis.Calculated: 49.5% F. Found: 50.4% F.

A mixture of 3.0 g. of the dihydrazino triazine and 4.0 g. of an epoxyresin (available commercially as Bakelite 2774) is placed in an oven at165 C. After about 1 hour, the mixture has gelled and after 3 hours ithas cured to a hard, glossy, oleophobic, transparent resin which shows aRockwell hardness of about 112.

EXAMPLE XII In a 500 ml. flask fitted with condenser and dropping funnelare placed 100 ml. of water, 15 g. (0.1 mole) of2,4-diamino-6-chloro-s-triazine and 45 g. (0.4 mole) of hexamethylenediamine and the mixture is refluxed for 2 hours during which time asolution of 4.0 g. (0.1 mole) of NaOH in ml. of water is added veryslowly. At the end of this time the reaction mixture is cooled and thecrystalline residue of 2,4-diamino-6-(6-aminohexyl amino)-s-triazine iscollected, thoroughly washed by resuspension in water and againcollected and air-dried. This material is recrystallized fromisopropanol or absolute ethanol and then melts at 175177 C.

Analysis.--Calculated: 48.0% C; 8.5% H; 43.5% N. Found: 47.9% C; 8.4% H;43.9% N. Other 2,4-diamino-6-(1r-aminoalkyl amino)-s-triazines areformed by analogous reactions.

In a 250 ml. flask fitted with reflux condenser are placed about 75 ml.of absolute ethanol, 6.8 g. (0.02 mole) of ethyl perfluorovalerate and4.5 g. (0.02 mole) of 2,4-diamino-6-(6-amino hexylamino)-s-triazineprepared as set forth above. The mixture is refluxed for 1.5 hours in asteam bath, the hot reaction mixture filtered to remove suspendedsolids, concentrated and cooled. The crystalline material whichprecipitates on cooling is recovered by filtration and washed withether. A further amount is obtained by evaporation and cooling of themother liquors. The crystalline 2,4 diamino-6-(-perfluorovaleramidohexylamino)-s-triazine thus prepared is recrystallized first fromethanol and then from aqueous methanol, and thereafter melts at about118 C. Analysis: calculated 18.8% N; 40.1% F; found, 18.9% N; 39.2% F.

10 EXAMPLE XIII In a 250 m1. flask fitted with a reflux condenser anddropping funnel are placed ml. of purified dry dioxane and 18 g. (0.08mole) of 2,4-diamino-6-(6-amino hexyl amino)-s-triazine prepared asdescribed in Example XII. In the dropping funnel is placed 20.0 g. (0.04mole) of perfluorooctanesulfonyl fluoride which, after the dioxanesolution in the flask has been heated to gentle boiling, is added veryslowly at such a rate that gentle refluxing is maintained by applicationof external heat and the somewhat exothermic reaction. This requiresabout 40 minutes after which refluxing is maintained for about 30minutes. After cooling the crystalline residue is collected and dried.Washing the precipitate with water removes the 2,4-diamino 6 (6-aminohexyl amino)-s-triazine, which can be recovered from the aqueouswashings. The residue not soluble in Water is crude 2,4-diamino-6-(6-perfluorooctanosulfonamidohexylamino) s triazine. Afterrecrystallization from ethanol, the latter melts sharply at about C.

Analysis.-Caluculated: 28.8% C; 45.6% F. Found: 29.4% C; 44.9% F.

A mixture of 7 g. of the crude2,4-diamino-6-(6-perfluorooctanesulfonamidohexylamino) s triazine withabout 5 ml. of 37% aqueous formaldehyde and a few drops of 10% sodiumhydroxide in 15 ml. of dioxane is refluxed for 1 hour. As a result thereis obtained a solution of the corresponding condensation polymer, whichis diluted with acetone and butanol and is then applied to the surfaceof a polyethylene terephthalate film and dried. The surface is thuscoated by polymer molecules with exposed fluorocarbon tails and is notwetted by toluene.

EXAMPLE XIV The S-(perfluorooctyl)-pentanoic acid prepared as describedin Example I is first converted to the acid chloride by treating withphosphorus pentachloride in slight excess and then to the amide bytreatment with an excess of ammonia. The white crystalline amide isdried and reduced to the amine with lithium aluminum hydride by theprocedure described in US. Patent 2,691,043 for perfluorinated acidamides. When the resultant 5-(perfluorooctyl)-amyl amine is then used inplace of the 1,1- dihydroperfluorooctanol for reaction with6-chloro-2,4- diamino-s-triazine in the procedure of Example I, there isobtained 2,4-diamino-6- 5-perfluorooctyl-amyl-amino -striazine.

Another use for the compounds of this invention and more particularlytheir formaldehyde condensates is as hardening agents foralkyl-urea-formaldehyde, and melamine-formaldehyde resins. Asimultaneous increase in the oiland water-repellency of the surfaces ofthe resins so hardened is produced because of the fluorocarbon chainsintroduced and chemically bound therein.

While the condensation of the monomers of the invention to form resinousproducts has been illustrated herein by the use of formaldehyde, it willbe apparent therefrom to those skilled in the art that other substancescan equally well be employed as aldehydic reactants for the purpose.Thus compounds capable of engendering formaldehyde can be used, e.g.paraformaldehyde and hexameth ylene tetramine. Other aldehydes can beemployed, such as acetaldehyde, furfural and the like. The disclosure ofDAlelio et al. in US. Patent Number 2,393,754 is illustrative of thealdehydes and derivatives thereof suitable for condensation with thesubstituted triazines of the invention.

What is claimed is:

1. Perfluoroalkyl-substituted triazines of the formula:

R R SO2N and Rt( 2) q wherein R is a perfiuorinated alkyl radical of4-12 carbon atoms, 11 is 1-12, R is selected from the group con sistingof hydrogen and lower alkyl and q is 1-13.

2. The compounds according to claim 1 wherein R --Z-- iS R SO NH(CH),,NH

and X and Y are NH 3. The compounds according to claim 1 wherein R1 Z isand X and Y are NH 4. The compounds according to claim 1 wherein R1-Z lSand X and Y are NH 5.2,4-diamino-6-(G-perfluorooctanesulfonamidohexylamino) -s triazine.

6. 2,4-dia1nino-6-(N-rnetllyl-perfluorooctanesulfonamido) -s-triazine.

7. 2,4-diamino-6-(N-methyl-perfluorobutanesulfonamido) -s- 'triazine.

12 8. 2,4-diarnino-6- 1, l-dihydroperfiuorooctoxy -s-triazine.

9. The product produced by refluxing together for from 1 to 4 hoursconcentrated aqueous formaldehyde and a triazine according to claim 1.

References Cited in the file of this patent UNITED STATES PATENTS2,165,265 Hubert et al July 11, 1939 2,328,958 DAlelio et a1 Sept. 7,1943 2,338,493 DAleilo et a1 Jan. 4, 1944 2,392,649 DAlelio et a1 Jan.8, 1946 2,418,336 DAlelio et a1 Apr. 1, 1947 2,508,323 Adams May 16,1950 2,510,503 Kropa June 6, 1950 2,513,264 Holm-Hansen June 27, 19502,523,470 Kropa et a1 Sept. 26, 1950 2,566,226 Mackay et a1 Aug. 28,1951 2,741,606 Holt et a1 Apr. 10, 1956 2,759,019 Brown et al Aug. 14,1956 2,764,574 Widmer et a1 Sept. 25, 1956 2,767,180 Winthrop et al Oct.16, 1956 2,803,615 Ahlbrecht et a1 Aug. 20, 1957 2,809,990 Brown et a1Oct. 15, 1957 2,822,347 Wohnsiedler Feb. 4, 1958 OTHER REFERENCESHodgins et al.: Industrial and Engineering Chemistry, volume 33, pages769771 (1941).

Garns et al.: British Plastics, pages 508514 (February 1943).

UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3128,272 April 7, 1964 Robert L Wear et a1 It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe 'said Letters Patentshould read as corrected below.

Column 3 line 33 for "2 606 797" read 2 666,797

columns 3 and l lines 38 to 49 for that portion of the equation readingread same lines 38 to 49, for that portion of the equation reading "R==CH '=-CH CH -GH NH" read R -CH -CH -CH -=CH NH column 8 line 3,, after"-dihydroperfluorooctoxy" insert a closing paren thesis; line 14 for "V"read e- IV --g line 22 for "IV" read 111 column 9 line 20 for "V" readIV line 34, for perfluoroctanesulfonamide)--" readperfluorooctanesulfon= amido) -n Signed and sealed this 15th day ofDecember 1964.,

Attest:

ERNEST WQ SWIDER EDWARD JL-BRENNER' Altesting' O fficer Commissioner ofPatents

1. PERFLUOROALKYL-SUBSTITUTED TRIAZINES OF THE FORMULA: